Method of controlling insects with adducts of hexahalocyclopentadiene with alkadienes



United States Patent METHOD OF CONTROLLING INSECTS WITH ADDUCTS OFHEXAHALOCYCLOPENTADIENE WITH ALKADIENES Edward D. Well, Lewiston, N.Y.,and John F. Porter, Morristown, N.J., assignors to Hooker Chemical Cor-I orafiion, Niagara Falls, N.Y., a corporation of New No Drawing.Original application Feb. 17, 1964, Ser. No. 345,066. Divided and thisapplication Nov. 30, 1966, Ser. No. 615,872

2 Claims. (Cl. 424-351) x x I CHzCHzCHzCHKCHzhCH=CH2 I OX2 X ICH2CHzCH2CH2(CE2)u I X OX2 0 2 I XI X wherein X is a halogen atom suchas chlorine or bromine, said halogen atoms being the same or differentand n is a number from zero to about 12.

Among the compounds within the present invention are the 1:1 and 1:2adducts of 1,7-octadiene and longer chain terminal diolefins containingfrom 8 to about 20 carbon atoms and preferably from 8 to about 16 carbonatoms such as 1,9-decadiene, 1,11-dodecadiene, 1,15-hexadecadiene and1,19-eicosadiene (hereinafter called a,a-alkadienes) withhexachlorocyclopentadiene, hexabromocyclopentadiene,bromopentachlorocyclopentadiene, dibromotetrachlorocy-clopentadiene,tribromotrichlorocyclopentadiene, tetrabromodifluorocyclopentadiene, andpentabromochlorocyclopentadiene, and the like. The preferred species forreasons of ease of manufacture, and activity are the 1:1 and 2:1 adductsof hexachlorocyclopentadiene with 1,7-octadiene.

Illustrative examples of some of the compounds embraced herein thusinclude those as represented by the following formulas, but theinvention is not intended to be limited thereto.

Br I (CH2)4CH=CH2 GClz B1 Br Br 01 I CHzCHzCHzCH I o1 I 013m CB12 I 01 II o1 Br Br 01 -CH2CH2CH2CH2CH=CE2 I CB1: or I c1 -omomomornon=om I CO1:or

or 01 01 I CH CH2OH1CHaCH2OI-IzCHzCH2 I 01 I 0012 0012 I 01 I I 01 0'101 01 c1 01 (I onlonzomonz I o1 I C171 0012 I 01 I I c1 01 or The 1:1adducts and 2:1 adducts are prepared by the Diels-Alder reaction ofhexahalocyclopentadiene, wherein the halogen atoms have an atomic weightbetween 34 and 81 with the appropriate dienes, it being understood thatthe Diels-Alder diene synthesis comprises the 1,4 addition to a diene ofan olefinic double bond.

The reaction is accomplished by heating together hexahalocyclopentadieneand the a,a-alkadiene at a temperature from about 40 degrees centigradeto 250 degrees Centigrade, and preferably at a temperature from 60degress Centigrade to 200 degrees centigrade in the liquid phase, for aperiod of time ranging from 10 minutes near the higher temperature toabout 10 days or more at the lower temperatures, the time beingdetermined at any tempertaure by observing the exact conversion usingdistillation analysis, gas chromatography, infrared spectrum, change ofrefractive index, or any other convenient means to measure conversion.

The molar ratio of hexahalocyclopentadiene to aptalkadiene will dependupon the product desired. Thus, if the 1:1 adduct is desired, 1 mole ofhexahalocyclopentadiene to 1 mole or more of a, x'-alkadiene areutilized, while if the 2:1 adduct is desired, two moles or more ofhexahalocyclopentadiene to one mole of a,a-alkadiene is generallyemployed. At most ratios at least some of each adduct is formed.

The 1:1 adducts, which are generally liquid, are best isolated andpurified by distillation although other methods known in this art can beutilized. The 1:2 adducts, which are generally crystalline solids, areconveniently filtered out and if desired, recrystallized. Further, bothproducts can be made simultaneously, if desired, and are easilyseparated by separation methods known in this art, such as distillation,filtration or combination of these methods.

The novel compounds of the present invetion have utility as pesticidesand flame retardant additives to polymers. The 1:1 adduct is preferablyutilized as the pesticide while the 1:2 adduct possesses flame retardantproperties when incorporated into resins. Specifically, the 1:2 adductsexemplified by the 1:2 Diels-Alder product of hexachlorocyclopentadienewith 1,7-octadiene possess remarkable flame retardant properties whenincorporated into resins, as will be more fully illustrated in theworking examples.

For flame-retardant purposes the compositions comprising the novelcompositions of the present invention can be admixed into the polymer byone of several methods known in this art. For example, the additives canbe introduced into the polymer while the latter is dissolved in asuitable solvent. This procedure is especially useful when it is desiredto mix the additives during the polymer manufacturing process. When thepolymer is subsequently recovered from the solvent, the additives areintermittently mixed with the polymer. Usually the additives are mixedwith the polymer in the molten state at temperatures that can range fromthe melting point to a temperature just below the decompositiontemperature of the polymer. Alternatively, the additives and polymer aredry blended in the finely divided state so that intimate mixture isobtained upon subsequent molding or extrusion.

Among the polymers in which the compounds of this invention are usefulare the homopolymers and copolymers of unsaturated aliphatic,cycloaliphatic and aromatic hydrocarbons, such as polyethylene,polypropylene, polybutene, ethylene propylene copolymers, copolymers ofethylene or propylene with other olefine, polybutadiene, polymers ofbutadiene, polyisoprene, natural or synthetic, polystyrene,polyvinylidene chloride, indene-courarone resins, polymers of acrylateesters and polymers of methacrylate esters, acrylate and methacrylateresins such as ethyl acrylate, n-butyl methacrylate, isobutylmethacrylate, ethyl methacrylate, and methylmethacrylate, alkyd resins,hydrocarbon resins from petroleum, isobutylene resins (polyisobutylene),isocyanate resins (polyurethanes), polyester resins such as polyesters(unsaturated) and polyester-elastomer and polyisobutylene, rubbers suchas natural rubber, synthetic polyisoprene, chlorinated rubber,polybutadiene, cyclized rubber, butadieneacrylonitrile rubberbutadiene-styrene rubber, and butyl rubber, neoprene rubber(polychloroprene), styrene resins (polystyrene), terpene resins, urearesins, vinyl resins such as vinyl acetal, vinyl acetate or vinylalcohol-acetate, vinyl acetate copolymer, vinyl alcohol, vinyl alkylether, vinyl methyl ether-maleic anhy'dride copolymer, vinyl chloride,vinyl butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone andvinylidene chloride copolymer and the like.

The fire retardant compound of the instant invention are desirablyincorporated into polymer materials in the range from about 5 to about50 percent by weight of the polymer composition, and preferably fromabout to about percent by weight. An antimony compound, such as antimonyoxide, can be used in amounts ranging from less than one to about 30percent by weight of the polymer composition and preferably from 5 toabout 20 percent by weight of the polymer composition to further enhanceflame retardant properties.

In their application as pesticides (especially as inseoticides) thecompounds of the invention, particularly the 1:1 adducts withhexahalocyclopentadiene are applied either pure or in a formulated stateat effective or pesticidal rates to the loci of the pests to becontrolled. Pesticidal rates generally will encompass 0.05 to 100 poundsper acre, the lower range being employed with the more sensitive speciesand where only short term control is needed, the higher range whereresistant species are involved or where long-duation control is desired.The concentrations in which the active insecticide is applied willgenerally be in the range of from 0.001 to 100 percent. Suitableformulations comprise mixtures with solvents, diluents, solid carriers,and surfactants. Suitable solvents include petroleum hydrocarbons suchas xylene, aromatic naphtha, and the like. Diluents include water(generally with an emulsifier). Solid carriers include clay,vermiculite, fertilizer, talc, wood flour and other mineral orcellulosic granules and powders. Suitable surfactants include the anioictype, exemplified by alkylarylsulfonates, the nonionic type, exemplifiedby polyethyleneoxide ethers of polyols or phenols and the cationic type,exemplified by long chain quaternary alkyl ammonium chlorides. Otherformulation variations will be evident to one skilled in the pesticideart. Other adjuvants such as attractants, bait substances, and otherpesticides may also be incorporated into the formulations.

The 1:1 adducts of the invention, having an unhindered olefinic doublebond, can be polymerized and copolymerized, for example, with propyleneand/or ethylene, using the catalysts known to the art for polymerizingpropylene and ethylene. The polymers so produced have the advantage ofpossessing flame-retardant properties.

In the examples, specification and claims, parts are by weight andtemperatures are in degrees centigrade, unless otherwise specified.

In order that those skilled in the art may better understand the presentinvention and the manner in which it may be practiced, the followingillustrated examples are given.

EXAMPLE 1 Preparation of 1:1 and 2:1 adducts ofhexachlorocyclopentadiene and octadiene-1,7

A mixture of 273 parts by weight of hexaohlorocyclopentadiene and 55parts by weight of octadiene-l,7 was heated on the steam bath for 2.5days, then cooled to 25 degrees centigrade. The 2:1 adduct partlycrystallized out and a sample was removed by filtration. The bulk of thereaction mirture was stripped under 0.1 mm. pressure to a pottemperature of degrees, the distillate consisting of excess unreacted1,7-octadiene and a small amount of unreacted hexachlorocyclopentadiene.The residue was dissolved in 600 parts of hot benzene, and the solutionwas cooled and filtered. The crystalline solids thus removed amounted toparts of colorless 2:1 adduct, of the formula CHzCHzCHzCHzl or con 0012or or o as a yellowish liquid distillate, boiling point l32139 degrees(0.45 mm.). The infrared spectrum showed a CH=CH group to be present.

Analysis.--Calculated for 13 14 6 Found: Cl, 55.7%.

EXAMPLE 2 In a manner similar to Example 1 otherhexahalocyclopentadienes and u,a-alkadienes are reacted, as shown:

and 1,7-0ctadiene and percent antimony oxide was blended in a ball millovernight, extruded at 325 degress Alkadiene (parts)Hcxahalocyclopentadiene Temp. Time Products (C.) (hrs.) 1,7-octadiene5,5-dibrorno-1,2,3,4-tetrachloro- 100 48 C1 cyclopentadiene (300). CHCH2 I OBI: C1 1/ Cl Cl -(cH2)i c1 l T C1 Cl 01 CI 1,9-decadiene(50)Hexachlorocyclopentadiene(300) 120 10 01 o /I\(CHZ)(CHCHZ GCl 01 I/ C1Cl 0 i om 01 (F012 1 (I301; 0 Cl 1,11-dodecadienc(50) ..do 140 5 C1 01 I(CH-z)aCH-CH O1 C1 01 om c1 C012 C012 01 l 01 C1 C1 1,19-cicosadiene(50)d0 160 1 O1 i -(cHi)m0H=cHz CC12 I 01 C1 Cl C I 2)1o- I G1 I C012 I CClzo1 Cl EXAMPLE 3 Fahrenheit, chopped into prills, and injection molded atInsecticidal activity of the 1:1 adduct of hexachlorocyclopentadiene and1,7-octadiene Adult houseflies (Musca domestica) were sprayed with an0.1 percent aqueous dispersion of the 1:1 adduct ofhexachlorocyclopentadiene and 1,7-0ctadiene as produced in Example 1.The percentage fly knockdown after two hours was 100 percent and thepercentage kill after 24 hours was 100 percent. Under similarconditions, the 1:1 adduct of hexachloropentadiene and butadiene gives anegligible kill.

The adduct of the 1,9-decadiene with hexachlorocyclopentadiene is foundto have similar activity, when tested against adult housefiies undersimilar conditions.

In Examples 4-6 the properties of the molded polymer compositions weretested in accordance with the standard American Society for TestingMaterial (ASTM) test procedures as follows:

EXAMPLE 4 Use of 2:1 adduct of hexachlorocyclopentadiene and 1,7-octadiene as flame retardant additive for a resin A compositioncontaining percent polypropylene, 30 percent of the 2:1 adduct ofhexachloroyclopentadiene 350 degrees Fahrenheit into Ms X /2 X 5 inchbars. The material molded easily and the bars were pure while in color.

Flame retardance tests An AST-M D-635-56T test was run on two of thebars described in the above paragraph. The results (outlined below)indicate that the composition is usefully fire 60 resistant.

Bar Burning Time Burning Time Length No. (see) After (see) After Burned,in.

First Ignition Second Ignition test utilizing compression moulding and arod 9 millimeters in diameter.

fectively fire-retardant composition. Of course, lesser proportions ofthe adduct are also useful in reducing the flammability of resins andplastics. Test results are given below:

Percent polypropylene 55 62. Percent 2:1 adduct ofhexachlorocyclopontadienc and 1,7-

octadiene s. 30 25 Percent antimony oxide" 15 12v 5 Burning timer (sed)4. 4 13.2

EXAMPLE 5 Effect on mechanical properties of 2:1hexachlorocyclopentadiene and 1,7-octadiene adduct Several mechanicalproperty tests were run on injectionmolded bars of a compositioncontaining 55 percent polypropylene, 30 percent l,7-octadienehexachlorocyclopentadiene adduct and percent antimony oxide. The resultsare shown in the next table. For comparison, data for pure polypropylenealso are given. The heat-distortion Comparison of heat aging behavior ofresin containing 2:1 hexachlorocyclopentadiene 1,7-octadiene adduct Thefollowing compositions were intimately blended and then were molded intoA3" x /2" x 5" test bars:

(1) of the 2:1 C Cl /1,7-octadiene adduct 40 15% Sb O 55% polypropylene(2) 25% 2:1 C Cl /butadiene adduct 12 /2 Sb O 62 /2% polypropylene Thebars were then heated at 120 degrees centigrade in an air-circulatingoven and the percent weight loss determined at various intervals. Theresults were as follows:

Weight Loss at Number of Days Composition; Indicated, percent The barsof Composition 1 retained substantially their original appearance andproperties.

When tested in accordance with the above procedures thehexabromocyclopentadiene, 1,9-decadiene adduct is found to have similarproperties.

While there have been described various embodiments of the invention,the methods and elements described are not intended to be understood aslimiting the scope of the invention. It is further intended that eachelement recited in any of the following claims is to be understood asreferring to all equivalent elements for accomplishing substantially thesame results in substantially the same or equivalent manner, it beingintended to cover the invention broadly in whatever form its principlemay be utilized.

What is claimed is:

1. A method for the control of insects which comprises applying aninsecticidally effective amount of the compound wherein X is a halogenchosen from the group consisting of bromine, chlorine and fluorine, andn is a number from zero to 12, together with a formulation adjuvantselected from the group consisting of solvents, diluents, solid carriersand surfactants.

References Cited UNITED STATES PATENTS 8/1952 Herzfeld et al. 260346.6

OTHER REFERENCES Ungnade et al.: Chemical Reviews, 1958, pp. 250,254-258.

ALBERT T. MEYERS, Primary Examiner.

RAMONA S. DORCAS, Assistant Examiner.

U.S. Cl. X.R. 260--648

1. A METHOD FOR THE CONTROL OF INSECTS WHICH COMPRISES APPLYING ANINSECTICIDALLY EFFECTIVE AMOUNT OF THE COMPOUND